Reactivity ratios and monomer partitioning in the microemulsion copolymerization of vinyl acetate and butyl acrylate

The true monomer reactivity ratios for the vinyl acetate/butyl acrylate system were determined with experimental data from the cumulative copolymer composition at low, intermediate, and high conversions and with the monomer partitioning among the aqueous, microemulsion droplet, and polymer particle phases taken into account. A mixture of sodium dodecyl sulfate and poly(ethylene oxide) (23) dodecyl ether (Brij-35; 3 : 1 w/w) was used as a stabilizer. Potassium persulfate was used as an initiator. The true values of the monomer reactivity ratios were 0.028 ±3.2 × 10-3 for vinyl acetate and 6.219 ± 3.1 × 10-1 for butyl acrylate, and these were in agreement with those reported in the literature for bulk copolymerizations but differed from values reported for other compartmentalized copolymerizations. Thus, these results indicate that the monomer partitioning and cumulative copolymer composition throughout the reaction have to be duly accounted for in the determination of monomer reactivity ratios in heterogeneous polymerizations. © 2008 Wiley Periodicals, Inc